KR102611583B1 - Molded body - Google Patents

Abstract

One embodiment of the present invention includes a resin substrate; Part or all of the surface of the substrate is covered with a hard coat; The first hard coat includes (A) 100 parts by mass of a polyfunctional (meth)acrylate, (B) 0.01 to 7 parts by mass of a water repellent, and (C) 0.01 to 10 parts by mass of a silane coupling agent, and does not contain inorganic particles. It is formed from a paint that does not; The second hard coat is a molded body formed from a paint comprising: (A) 100 parts by mass of a polyfunctional (meth)acrylate and (D) 50 to 300 parts by mass of inorganic fine particles having an average particle size of 1 to 300 nm. . Another embodiment of the present invention includes a resin substrate; Part or all of the surface of the substrate is covered with a hard coat, the first hard coat is formed of a paint that does not contain inorganic particles, and the second hard coat is formed of a paint that contains inorganic particles; It is a molded article in which (i) the total light transmittance is 85% or more, and (ii) the pencil hardness of the surface of the first hard coat is 5H or more.

Description

Molded body {MOLDED BODY}

The present invention relates to molded bodies. More specifically, the present invention relates to a molded body having excellent surface hardness.

Typically, to impart functions such as surface hardness, wear resistance, durability, stain resistance, or designability to molded bodies such as housings of home appliances or information electronic devices, or dashboards of automobiles, the substrate of the article is used. The surface is often coated with a curable resin paint such as acrylic resin, melamine resin, isocyanate resin, or urethane resin to form a coat. There are many limitations in techniques for improving wear resistance by forming a coat of curable resin paint (see, for example, Patent Documents 1 and 2). However, the surface hardness and abrasion resistance of these coats are still insufficient, and a molded body is needed that can maintain its surface characteristics even after repeated wiping with a cloth or the like.

JP 2014-043101 A JP 2014-040017 A

The object of the present invention is to provide a molded body with excellent surface hardness. Another object of the present invention is to provide a three-dimensional molded body preferably having excellent surface hardness and wear resistance.

As a result of intensive research, the present inventor discovered that the above-mentioned problem can be achieved by forming two types of specific hard coats in the molded body.

That is, various aspects of the present invention are as follows.

[One].

A molded body comprising a resin substrate as follows:

Part or all of the surface of the substrate is covered with a hard coat,

The hard coat includes, from the surface layer side, a first hard coat layer and a second hard coat layer,

The first hard court is:

(A) 100 parts by mass of polyfunctional (meth)acrylate;

(B) 0.01 to 7 parts by mass of a water repellent; and

(C) 0.01 to 10 parts by mass of a silane coupling agent

It is formed of a paint that contains and does not contain inorganic particles,

The second hard court is:

(A) 100 parts by mass of polyfunctional (meth)acrylate; and

(D) 50 to 300 parts by mass of inorganic fine particles having an average particle size of 1 to 300 nm.

A molded body formed from a paint containing a.

[2].

The molded article according to [1] above, wherein (C) the silane coupling agent contains at least one selected from the group consisting of a silane coupling agent having an amino group and a silane coupling agent having a mercapto group.

[3].

The molded article according to [1] or [2] above, wherein (B) the water repellent agent contains a (meth)acryloyl group-containing fluoropolyether water repellent agent.

[4].

The molded article according to any one of the above [1] to [3], wherein the second hard coat forming paint further contains (E) 0.01 to 1 part by mass of a leveling agent.

[5].

The molded body according to any one of the above [1] to [4], wherein the first hard coat forming paint further contains (F) 0.1 to 15 parts by mass of resin fine particles having an average particle size of 0.5 to 10 μm.

[6].

The molded article according to any one of the above [1] to [5], wherein the first hard coat has a thickness of 0.5 to 5 μm.

[7].

The molded article according to any one of [1] to [6] above, wherein the second hard coat has a thickness of 5 to 30 μm.

[8].

A molded body comprising a resin substrate as follows:

Part or all of the surface of the substrate is covered with a hard coat,

The hard coat includes, from the surface layer side, a first hard coat layer and a second hard coat layer,

The first hard coat is formed from a paint containing no inorganic particles,

The second hard coat is formed from a paint containing inorganic particles,

A molded body satisfying the following (i) and (ii):

(i) total light transmittance of at least 85%; and

(ii) Pencil hardness on the first hard coat surface of 5H or greater.

[9].

A molded body comprising a resin substrate as follows:

Part or all of the surface of the substrate is covered with a hard coat,

The hard coat includes, from the surface layer side, a first hard coat layer and a second hard coat layer,

The first hard coat is formed from a paint containing no inorganic particles,

The second hard coat is formed from a paint containing inorganic particles,

Molded articles satisfying the following (iii) and (iv):

(iii) a water contact angle at the first hard coat surface of at least 100°; and

(iv) Water contact angle on the first hard coat surface after 20,000 reciprocating wipes on cotton, greater than 100°.

[10].

The molded body according to any one of [1] to [9] above, wherein the substrate has a three-dimensional shape.

[11].

The molded body according to any one of [1] to [10] above, wherein the end portion has a chamfered shape.

[12].

An article comprising the molded body according to any one of [1] to [11] above.

[13].

A method for producing a molded body according to any one of [1] to [11] above, comprising the following steps:

(1a) manufacturing a substrate by molding the resin sheet in three dimensions;

(2) forming a second hard coat on part or all of the surface of the substrate obtained in step (1a); and

(3) Forming a first hard coat on the surface of the second hard coat formed in step (2).

[14].

A method for producing a molded body according to any one of [1] to [11] above, comprising the following steps:

(1b) manufacturing a substrate by molding a thermoplastic resin;

(2) forming a second hard coat on part or all of the surface of the substrate obtained in step (1b); and

(3) Forming a first hard coat on the surface of the second hard coat formed in step (2).

[15].

A method for producing a molded body according to any one of [1] to [11] above, comprising the following steps:

(1c) manufacturing a substrate by molding a curable resin;

(2) forming a second hard coat on part or all of the surface of the substrate obtained in step (1c); and

(3) Forming a first hard coat on the surface of the second hard coat formed in step (2).

[16].

A method for producing the article described in [12] above, comprising the following steps:

Manufacturing a molded body by the method described in any one of [13] to [15] above; and

(4) manufacturing an article using the molded body thus obtained.

The molded body of the present invention has excellent surface hardness. The preferred molded body of the present invention has an arbitrary three-dimensional shape, and has excellent surface hardness and wear resistance. Therefore, the molded body of the present invention can be suitably used as a housing for home appliances such as televisions, refrigerators, washing machines, vacuum cleaners, microwave ovens, or air conditioners. The molded body of the present invention can also be suitably used as a housing for information electronic devices such as smart phones, tablet terminals, car navigation systems, digital cameras, or personal computers, curved display faceplates, etc. Moreover, the molded body of the present invention can be suitably used as an automobile instrument panel, window, shift knob, etc.

Figure 1 shows a top view (a) and a side view (b) illustrating a substrate manufactured in an example.
Figure 2 is a diagram explaining the manufacture of a substrate by a vacuum forming method.
Figure 3 is a cross-sectional view showing an example of end face processing of a molded body.
Fig. 4 is a conceptual diagram of the apparatus used for manufacturing the resin sheet in the examples.

The term “resin” referred to herein is used as a term that includes a resin mixture containing two or more resins and a resin composition containing component(s) other than the resin. As used herein, the term “sheet” is used to include film and board.

1. Substrate

The molded body of the present invention has a resin substrate. The substrate gives the molded body of the present invention a desired shape. The substrate preferably imparts mechanical properties such as impact resistance, strength, and rigidity to the molded body of the present invention.

The shape of the substrate is not particularly limited, but may be any desired shape. The shape of the substrate may be a planar shape. However, when the molded body of the present invention is used for housings of home appliances, dashboards of automobiles, etc., the shape is usually a three-dimensional shape.

The manufacturing method of the substrate is not particularly limited, but the substrate can be manufactured by molding any resin by any method.

1-1. Substrate manufactured by forming a resin sheet in three dimensions

Preferred examples of methods for manufacturing the substrate include methods of subjecting the resin sheet to so-called three-dimensional molding, such as membrane pressing, compression molding, vacuum forming, or vacuum compression molding.

The thickness of the resin sheet is not particularly limited, but from the viewpoint of maintaining the strength and rigidity required as a substrate for a molded body, it is usually 0.1 mm or more, preferably 0.2 mm or more, more preferably 0.5 mm or more, and even more preferably It may be 0.8 mm or more, most preferably 1 mm or more. At the same time, the thickness of the resin sheet may be usually 10 mm or less, preferably 6 mm or less, and more preferably 3 mm or less from the viewpoint of meeting the requirement for lightweighting of the article and three-dimensional moldability. The thickness of the resin sheet is usually 0.1 mm or more and 10 mm or less, preferably 0.1 mm or more and 6 mm or less, 0.1 mm or more and 3 mm or less, 0.2 mm or more and 10 mm or less, 0.2 mm or more and 6 mm or less, and 0.2 mm or more. mm or more and 3 mm or less, 0.5 mm or more and 10 mm or less, 0.5 mm or more and 6 mm or less, 0.5 mm or more and 3 mm or less, 0.8 mm or more and 10 mm or less, 0.8 mm or more and 6 mm or less, 0.8 mm or more It may be from 3 mm to 3 mm, from 1 mm to 10 mm, from 1 mm to 6 mm, or from 1 mm to 3 mm.

The tensile modulus of elasticity of the resin sheet is not particularly limited, but may be preferably 1500 MPa or more, more preferably 1800 MPa or more from the viewpoint of maintaining the strength and rigidity required as a substrate for a molded body. The upper limit of the tensile modulus is not particularly specified. However, the tensile modulus is usually up to about 10000 MPa within the available range. The tensile modulus was measured according to JIS K7127:1999 under the conditions of test specimen type 1B and a tensile speed of 50 mm/min.

The glass transition temperature of the resin constituting the resin sheet is not particularly limited, but is usually 80°C or higher, preferably 80°C or higher, from the viewpoint of maintaining heat resistance (including both the heat resistance necessary when manufacturing the molded body and the heat resistance necessary when using the molded body). It may be 90°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher. Incidentally, when the resin sheet contains two or more types of resins as constituent resins, it is preferable that the resin with the lowest glass transition temperature among these resins satisfies the above range.

The glass transition temperature of the resin constituting the resin sheet is usually 170°C or lower, preferably 160°C or lower, and more preferably 155°C or lower from the viewpoint of processing ability during three-dimensional molding to obtain a substrate. Incidentally, when the resin sheet contains two or more types of resins as constituent resins, it is preferable that the resin with the highest glass transition temperature among these resins satisfies the above range.

The glass transition temperature of the resin constituting the resin sheet is preferably 80°C or higher to 170°C or lower, more preferably 80°C or higher to 160°C or lower, 80°C or higher to 155°C or lower, 90°C or higher to 170°C or lower, 90°C or higher to 160°C or lower, 90°C or higher to 155°C or lower, 100°C or higher to 170°C or lower, 100°C or higher to 160°C or lower, 100°C or higher to 155°C or lower, 110°C or higher to 170°C or lower, 110°C It may be above 160°C or below, or above 110°C and below 155°C.

Here, the glass transition temperature was determined by using a Diamond DSC type differential scanning calorimeter from [Perkin Elmer Japan Co., Ltd], heating the sample to 200°C at a temperature-rise rate of 50°C/min, and heating the sample at 200°C for 10 minutes. minutes, then the sample was cooled to 50°C at a temperature-fall rate of 20°C/min, the sample was held at 50°C for 10 minutes, and then the sample was cooled to 200°C at a temperature-rise rate of 20°C/min. The midpoint glass transition temperature is calculated by plotting according to Figure 2 of ASTM D3418 for the glass transition appearing in the curve measured in the last temperature-rise method of the temperature program for heating to .

Examples of resin sheets include polyester resins such as aromatic polyester or aliphatic polyester; Acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, or vinyl cyclohexane-methyl (meth)acrylate copolymer; poly(meth)acrylimide resin; polycarbonate resins such as aromatic polycarbonates or aliphatic polycarbonates; Polyolefin resins such as polyethylene, polypropylene, polybutene-1, or poly-4-methyl-pentene-1; Cellulose resins such as cellophane, triacetylcellulose, diacetylcellulose, or acetylcellulose butyrate; Styrene resins, such as polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene-ethylene-propylene-styrene copolymer, styrene-ethylene-ethylene-propylene -styrene copolymer, or styrene-ethylene-butadiene-styrene copolymer; Cyclic hydrocarbon resins such as ethylene-norbornene copolymers; polyamide resins such as nylon 6, nylon 66, nylon 12, or nylon 11; polyvinyl chloride resins, such as polyvinyl chloride or vinyl chloride-vinyl acetate copolymer; polyvinylidene chloride resin; Fluorine-containing resins such as polyvinylidene fluoride; Resin sheets formed from polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, polyimide, polyurethane, polyetherimide, polysulfone, polyethersulfone polyacrylate resin, and polymer type urethane acrylate resin. These sheets include unstretched sheets, uniaxially extended sheets, and biaxially extended sheets. These sheets also include laminated sheets obtained by laminating two or more layers of one or more types thereof. Additionally, these resin sheets may be transparent or may be colored with any colorant.

When the resin sheet is a laminated sheet, the lamination method is not limited, but lamination can be performed by any method. Examples thereof include a method of obtaining each resin sheet by any method and then subjecting the resulting resin sheet to dry lamination or heat lamination; Each constituent material is melted in an extruder, and a laminated sheet is obtained by T-die co-extrusion using the feed block method, multi-manifold method, or stack plate method. method; an extrusion lamination method of obtaining at least one resin sheet by any method and then melting and extruding another resin sheet on the resin sheet; Melting and extruding the constituent materials on an arbitrary film substrate, or applying and drying a paint containing the constituent materials and a solvent therefor, peeling off the formed resin sheet from the film substrate, and transferring the resin sheet onto another resin sheet. method; and methods of combining two or more of the above methods.

Among these sheets, from the viewpoint of mechanical properties and surface hardness, preferred examples of resin sheets include:

(a1) Acrylic resin sheet;

(a2) aromatic polycarbonate resin sheet;

(a3) polyester resin sheets (excluding resin sheets formed of acrylic resin or aromatic polycarbonate resin), and

(a4) A laminated sheet formed of any one or two or more of the resin sheets (a1) to (a3).

(a1) The acrylic resin sheet mainly contains an acrylic resin, such as polymethyl methacrylate or polyethyl methacrylate (usually more than 50% by mass, preferably more than 60% by mass, more preferably more than 70% by mass). It is a sheet formed of a resin composition.

Examples of acrylic resins include (meth)acrylate (co)polymers, copolymers of comonomers containing (meth)acrylates, and modified forms thereof. Note that the term (meth)acrylic means acrylic or methacrylic. The term (co)polymer refers to a polymer or copolymer.

Examples of (meth)acrylate (co)polymers are polymethyl (meth)acrylate, polyethyl (meth)acrylate, polypropyl (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate. -butyl (meth)acrylate copolymer, and ethyl (meth)acrylate-butyl (meth)acrylate copolymer.

Examples of copolymers of comonomers containing (meth)acrylates include ethylene-methyl (meth)acrylate copolymer, styrene-methyl (meth)acrylate copolymer, vinyl cyclohexane-methyl (meth)acrylate copolymer. , maleic anhydride-methyl (meth)acrylate copolymer, and N-substituted maleimide-methyl (meth)acrylate copolymer.

Examples of modified forms include polymers in which the lactone ring structure is introduced by an intramolecular cyclization reaction; Polymers in which glutaric anhydride is introduced by an intramolecular cyclization reaction; and polymers (hereinafter also referred to as “poly(meth)acrylimide resins”) in which the imide structure is introduced by reaction with an imidizing agent (e.g., methylamine, cyclohexylamine, or ammonia). Includes.

Poly(meth)acrylimide resin adopts the characteristics of excellent heat resistance and excellent dimensional stability derived from polyimide resin, and maintains the high transparency, high surface hardness, and high rigidity derived from acrylic resin, and has a light yellow to reddish brown color. It is a thermoplastic resin obtained by overcoming the disadvantage of color. Such poly(meth)acrylimide resin is described, for example, in JP 2011-519999 A. The term poly(meth)acrylimide herein means polyacrylimide or polymethacrylimide. Commercially available examples of poly(meth)acrylimide resin include “PLEXIMID TT50” (trade name) and “PLEXIMID TT70” from Evonik Industries AG.

As an acrylic resin, these compounds can be used alone or in a mixture of two or more thereof.

Preferred examples of optional components that can be contained in the acrylic resin include core-shell rubber. In an amount of 0 to 40 parts by mass (100 to 60 parts by mass of acrylic resin), preferably 0 to 30 parts by mass (100 to 70 parts by mass of acrylic resin), relative to the total amount of 100 parts by mass of acrylic resin and core-shell rubber. ) By using core-shell rubber in an amount of (a1), the machinability and impact resistance of the acrylic resin sheet can be improved.

Examples of core-shell rubbers include methacrylate-styrene/butadiene rubber graft copolymer, acrylonitrile-styrene/butadiene rubber graft copolymer, acrylonitrile-styrene/ethylene-propylene rubber graft copolymer, and acrylonitrile-styrene. /acrylate graft copolymer, methacrylate/acrylate rubber graft copolymer, and methacrylate-acrylonitrile/acrylate rubber graft copolymer. As core-shell rubber, these compounds can be used alone or in mixtures of two or more thereof.

Examples of other optional components that may be contained in the acrylic resin include thermoplastic resins other than acrylic resin and core-shell rubber; Pigments, inorganic fillers, organic fillers, and resin fillers; and additives such as lubricants, antioxidants, weathering stabilizers, heat stabilizers, mold release agents, antistatic agents, nucleating agents, or surfactants. The mixing amount of the optional component(s) may be usually 25 parts by mass or less, preferably about 0.01 to 10 parts by mass, based on 100 parts by mass of the total amount of acrylic resin and core-shell rubber.

(a2) The aromatic polycarbonate resin sheet is a sheet formed of a resin mainly containing aromatic polycarbonate resin (usually more than 50% by mass, preferably more than 70% by mass, more preferably more than 90% by mass). .

Examples of aromatic polycarbonate resins include aromatic dihydroxy compounds such as bisphenol A, dimethyl bisphenol A, or 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and phosgene. polymers obtained by interfacial polymerization methods; and aromatic dihydroxy compounds such as bisphenol A, dimethyl bisphenol A, or esters between 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and carbonate diesters such as diphenyl carbonate. Includes polymers obtained by exchange reactions. As an aromatic polycarbonate resin, these compounds can be used alone or in a mixture of two or more thereof.

Preferred examples of optional components that can be contained in the aromatic polycarbonate resin include core-shell rubber. The core-shell rubber is preferably used in an amount of 0 to 30 parts by mass (100 to 70 parts by mass of aromatic polycarbonate resin) relative to 100 parts by mass of the total amount of aromatic polycarbonate resin and core-shell rubber. By using it in an amount of 0 to 10 parts by mass (100 to 90 parts by mass of aromatic polycarbonate resin), the machinability and impact resistance of the (a2) aromatic polycarbonate resin sheet can be improved.

Examples of core-shell rubbers include methacrylate-styrene/butadiene rubber graft copolymer, acrylonitrile-styrene/butadiene rubber graft copolymer, acrylonitrile-styrene/ethylene-propylene rubber graft copolymer, and acrylonitrile-styrene. /acrylate graft copolymer, methacrylate/acrylate rubber graft copolymer, and methacrylate-acrylonitrile/acrylate rubber graft copolymer. As core-shell rubber, these compounds can be used alone or in mixtures of two or more thereof.

The aromatic polycarbonate resin includes thermoplastic resins other than aromatic polycarbonate resin and core-shell rubber, to the extent that it is not contrary to the purpose of the present invention; Pigments, inorganic fillers, organic fillers, and resin fillers; Additives such as lubricants, antioxidants, weathering stabilizers, heat stabilizers, mold release agents, antistatic agents, or surfactants; You can include additional ones if you wish. The mixing amount of the optional component(s) may generally be about 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the aromatic polycarbonate resin and core-shell rubber.

(a3) The polyester resin sheet is a polyester resin such as polyethylene terephthalate (usually more than 50% by mass, preferably 80% by mass or more, more preferably 90% by mass or more) ((a1) acrylic resin sheet and (a2) ) is a sheet formed of a resin mainly containing (excluding aromatic polycarbonate resin sheets). The polyester resin sheet includes a non-extended sheet, a uniaxially extended sheet, and a biaxially extended sheet. Polyester resin sheets also include laminated sheets obtained by laminating two or more layers of one or more types thereof.

(a3) The polyester resin sheet is preferably a resin mainly containing an amorphous or low crystallinity aromatic polyester resin (usually more than 50% by mass, preferably 80% by mass or more, more preferably 90% by mass or more). It is a sheet formed of.

Examples of amorphous or low crystallinity aromatic polyester resins include polyester copolymers formed with aromatic polycarboxylic acid components, such as terephthalic acid, isophthalic acid, orthophthalic acid, or naphthalene dicarboxylic acid, and polyhydric alcohol components such as ethylene glycol. , diethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1 , 3-propanediol, or 1,4-cyclohexanedimethanol.

Examples of amorphous or low crystallinity aromatic polyester resins include 50 mol% of terephthalic acid, 30 to 40 mol% of ethylene glycol, and 10 to 20 mol% of 1,4-cyclo, relative to a total amount of 100 mol% of monomers. glycol-modified polyethylene terephthalate (PETG), including hexanedimethanol; Glycol-modified polycyclohexylenedimethylene terephthalate (PCTG) comprising 50 mol% of terephthalic acid, 16 to 21 mol% of ethylene glycol, and 29 to 34 mol% of 1,4-cyclohexanedimethanol; Acid-modified polycyclohexylenedimethylene terephthalate (PCTA) comprising 25 to 49.5 mol% of terephthalic acid, 0.5 to 25 mol% of isophthalic acid, and 50 mol% of 1,4-cyclohexanedimethanol; 30 to 45 mole % terephthalic acid, 5 to 20 mole % isophthalic acid, 35 to 48 mole % ethylene glycol, 2 to 15 mole % neopentyl glycol, less than 1 mole % diethylene glycol, and less than 1 mole % acid-modified and glycol-modified polyethylene terephthalate containing bisphenol A; and 45 to 50 mol% of terephthalic acid, 5 to 0 mol% of isophthalic acid, 25 to 45 mol% of 1,4-cyclohexanedimethanol, and 25 to 5 mol% of 2,2,4,4,-tetra. and one or a mixture of two or more selected from acid-modified and glycol-modified polyethylene terephthalate, including methyl-1,3-cyclobutanediol.

Here, polyesters with a heat of fusion of 10 J/g or less are defined as amorphous polyesters, and polyesters with a heat of fusion of more than 10 J/g to 60 J/g or less are defined as low crystalline polyesters. . The heat of fusion was measured using a Diamond DSC type differential scanning calorimeter from [Perkin Elmer Japan Co., Ltd] by holding the sample at 320°C for 5 minutes and then lowering the sample to -50°C at a temperature-fall rate of 20°C/min. A second fusion curve (i.e. the final temperature- fusion curve measured in the ascending method).

If desired, the polyester resin may contain other component(s) as long as they do not conflict with the purpose of the present invention. Examples of optional components that may be contained include thermoplastic resins other than polyester resins; Pigments, inorganic fillers, organic fillers, and resin fillers; and additives such as lubricants, antioxidants, weathering stabilizers, heat stabilizers, mold release agents, antistatic agents, or surfactants. The mixing amount of the optional component(s) may be usually 25 parts by mass or less, preferably about 0.01 to 10 parts by mass, based on 100 parts by mass of the polyester resin.

Preferred examples of optional components that may be contained in the polyester resin include core-shell rubber. By using core-shell rubber, the impact resistance of the (a3) polyester resin sheet can be improved.

Examples of core-shell rubbers include methacrylate-styrene/butadiene rubber graft copolymer, acrylonitrile-styrene/butadiene rubber graft copolymer, acrylonitrile-styrene/ethylene-propylene rubber graft copolymer, and acrylonitrile-styrene. /acrylate graft copolymer, methacrylate/acrylate rubber graft copolymer, and methacrylate-acrylonitrile/acrylate rubber graft copolymer. As core-shell rubber, these compounds can be used alone or in mixtures of two or more thereof.

The mixing amount of core-shell rubber is preferably 0.5 parts by mass or more per 100 parts by mass of the polyester resin in order to improve impact resistance. Additionally, when manufacturing a transparent substrate, the mixing amount of core-shell rubber may be preferably 5 parts by mass or less, more preferably 3 parts by mass or less, in order to maintain transparency.

For example, the laminated sheet (a4) formed from any one or more of the resin sheets (a1) to (a3) can be extruded using any co-extrusion device such as a feed block type, multi-manifold type, or stack plate type. By carrying out co-extrusion film formation to obtain the desired layer arrangement, any one or more of the resin sheets (a1) to (a3) are obtained using any film forming apparatus, and then the resulting resin sheet(s) are By applying heat lamination or dry lamination to obtain the desired layer arrangement; Alternatively, it can be obtained by obtaining any one of the resin sheets (a1) to (a3) using any film forming apparatus, and then applying the resulting resin sheet as the substrate to extrusion lamination to obtain the desired layer arrangement. .

In the resin sheet, a printed layer may, if desired, be provided on the surface on which the second hard coat is formed to improve design feel. When the resin sheet is a transparent resin sheet, the printed layer may be provided on a surface opposite to the surface on which the second hard coat is formed. The printed layer is provided to impart high designability to the molded body of the present invention. The printed layer can be formed by printing any pattern using any ink and any printing equipment.

The printed layer can be formed wholly or partially on the desired surface of the resin sheet directly or through an anchor coat. The printed layer can be formed on the surface of an optional resin film and laminated directly or through an anchor coat onto the desired surface of the resin sheet. In this case, the optional resin film can be laminated as is or can be removed. Examples of patterns include metal-like patterns, such as hair lines, wood grain patterns, stone mesh patterns that imitate rock surfaces such as marble, woven patterns that imitate fabric or fabric-like patterns, and tile stitches. Includes stitch patterns, bricklaying patterns, parquet patterns, and patchwork. As a printing ink, ink obtained by suitably mixing pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, etc. with a binder can be used. Examples of binders include resins such as polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylate copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamide resins, butyral. Resins, polystyrene resins, nitrocellulose resins, or cellulose acetate resins, and resin compositions thereof. Additionally, to provide a metal-like design, aluminum, tin, titanium, indium, oxides thereof, etc. may be deposited, in whole or in part, directly or through an anchor coat on the desired surface of the resin sheet by known methods. You can.

A method for manufacturing a substrate by a vacuum forming method using a resin sheet will be described. Figure 1 illustrates an example of a substrate manufactured by the vacuum forming method in the examples described below (Figure 1(a) is a top view and Figure 1(b) is a side view). Figure 2 illustrates an example of manufacturing a substrate by the vacuum forming method. First, the resin sheet 6 is heated and softened using an infrared heater 7 or the like (FIG. 2(a)). Then, the softened resin sheet 6 is removed from the infrared heater 7, and the upper surface of the forming die 8 is quickly covered with the resin sheet 6 (FIG. 2(b)). Then, the space 9 between the resin sheet 6 and the molding die 8 is depressurized, and the resin sheet 6 is brought into close contact with the molding die 8 to obtain the substrate 10 (Figure 2 ( c)). The pressure in the space 9 is preferably 10 kPa or less, more preferably 1 kPa or less, from the viewpoint of bringing the resin sheet 6 and the molding die 8 sufficiently close to each other without leaving air between them. . From the viewpoint of adhesion, a smaller pressure in the space 9 is more desirable due to greater adhesion. Meanwhile, in practice, the lower limit of the pressure in the space 9 may be about 10 ^-5 KPa, taking into account the increase in cost in the mechanical strength of the resin sheet 6 and the acceleration for reducing the pressure in the space 9.

1-2. Substrates manufactured by thermoplastic molding

Preferred examples of methods for manufacturing the substrate include injection molding, blow molding, and extrusion molding of thermoplastic resin. Among the above methods, injection molding is preferable from the viewpoint of freedom of shape. Here, injection molding also includes insert molding. As the resin sheet to be inserted into the molding die, the sheet described above can be used.

The thermoplastic resin for constituting the substrate is not particularly limited, but any thermoplastic resin may be used. The thermoplastic resin for constituting the substrate is not limited as long as the thermoplastic resin is preferably applicable to at least one of injection molding, blow molding, and extrusion molding, and more preferably to injection molding.

Examples of thermoplastic resins include polyester resins such as aromatic polyesters or aliphatic polyesters; Acrylic resin; polycarbonate resin; poly(meth)acrylimide resin; polyolefin resins such as polyethylene, polypropylene, or polymethylpentene; Cellulose resins such as cellophane, triacetylcellulose, diacetylcellulose, or acetylcellulose butyrate; Styrene resins, such as polystyrene, acrylonitrile-styrene copolymer resin (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), styrene-ethylene-propylene-styrene copolymer, styrene-ethylene-ethylene-propylene -styrene copolymer, or styrene-ethylene-butadiene-styrene copolymer; polyvinyl chloride resin; polyvinylidene chloride resin; Fluorine-containing resins such as polyvinylidene fluoride; Includes polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyurethane, polyetherimide, polysulfone, and polyethersulfone. As thermoplastic resins, these compounds can be used alone or in mixtures of two or more thereof.

When the molded body of the present invention is used for housings of home appliances or information electronic devices, dashboards of automobiles, etc., among these thermoplastic resins, resins having excellent mechanical properties such as impact resistance, strength, and rigidity are preferred. Examples of such thermoplastic resins described above include acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, or vinyl cyclohexane-methyl (meth)acrylate copolymers; Styrene resins, such as polystyrene, acrylonitrile-styrene copolymer, or acrylonitrile-butadiene-styrene copolymer (ABS resin); Aromatic polyester resin; Aromatic polycarbonate resin; and polyolefin resins such as polyethylene or polypropylene.

As thermoplastic resins, these compounds can be used alone or in mixtures of two or more thereof.

Thermoplastic resins may, to the extent not contrary to the purpose of the present invention, contain components other than the thermoplastic resin, such as antioxidants such as phosphorus type, phenol type, or sulfur type; Weathering agents, such as anti-aging agents, light stabilizers, or ultraviolet absorbers; copper inhibitor; Lubricants such as modified silicone oils, silicone oils, waxes, acid amides, fatty acids, or fatty acid metal salts; Nucleating agents such as aromatic phosphate metal salt type or gelol type; Antistatic agents such as glycerin fatty acid esters; Fillers such as calcium carbonate, talc, magnesium hydroxide, mica, clay, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), titanium oxide, cellulose fibers, glass fibers, or carbon black; organic flame retardants; and an inorganic flame retardant, if desired.

1-3. Substrate manufactured by curable resin molding

A preferred example of a method for manufacturing a substrate includes a method of injecting a curable resin into a die having a desired shape and curing the curable resin.

The curable resin for constructing the substrate is a resin that can be cured with heat or active energy rays. The curable resin is not particularly limited, but any curable resin can be used. Examples of curable resins include resins having two or more reactive functional groups in one molecule; and a resin composition formed of at least one selected from a resin and an isocyanate curing agent (i.e., a compound having two or more isocyanate groups (-N=C=O) in one molecule), a photopolymerization initiator, an organic peroxide, and the like. Examples of reactive functional groups include amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, isocyanate groups, alkoxy groups, acyloxy groups, and halogen groups.

Examples of curable resins include activated energy radiation-curable resins; and an active energy ray-curable resin composition comprising the resin together with an isocyanate curing agent (i.e., a compound having two or more isocyanate groups (-N=C=O) in one molecule) and/or a photopolymerization initiator. Active energy radiation-curable resins are resins that can be polymerized and cured by active energy radiation, such as ultraviolet rays or electron beams.

Examples of active energy radiation-curable resins include (meth)acryloyl group-containing prepolymers or oligomers such as polyurethane (meth)acrylate, polyester (meth)acrylate, polyacrylic (meth)acrylate, epoxy (meth)acrylate, ) acrylate, polyalkylene glycol poly(meth)acrylate, or polyether (meth)acrylate; (meth)acryloyl group-containing monofunctional reactive monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate Latex, phenyl cellosolve (meth)acrylate, 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, or trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone or styrene; (meth)acryloyl group-containing bifunctional reactive monomers such as diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene Glycol di(meth)acrylate, 2,2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl) propane, or 2,2'-bis(4-(meth)acryloyloxypolypropyleneoxy phenyl) propane; (meth)acryloyl group-containing trifunctional reactive monomers, such as trimethylolpropane tri(meth)acrylate or trimethylolethane tri(meth)acrylate; (meth)acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra(meth)acrylate; (meth)acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth)acryloyl group-containing octafunctional reactive monomers such as tripentaerythritol acrylate; and polymers (oligomers or prepolymers) containing one or more of these monomers as constituent monomers. As an active energy radiation-curable resin, these compounds can be used alone or in mixtures of two or more thereof. It should be noted that the term (meth)acrylate is used herein to mean either acrylate or methacrylate.

Examples of isocyanate curing agents include methylenebis-4-cyclohexylisocyanate; Polyisocyanates, such as the trimethylolpropane adduct form of tolylene diisocyanate, the trimethylolpropane adduct form of hexamethylene diisocyanate, the trimethylolpropane adduct form of isophorone diisocyanate, the isocyanurate form of tolylene diisocyanate. , the isocyanurate form of hexamethylene diisocyanate, the isocyanurate form of isophorone diisocyanate, or the biuret form of hexamethylene diisocyanate; and urethane crosslinkers such as blocked isocyanates of polyisocyanates. These isocyanate curing agents can be used alone or in combination of two or more types thereof. In crosslinking, catalysts such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added if necessary.

Examples of photopolymerization initiators are benzophenone compounds such as benzophenone, methyl-o-benzoyl benzoate, 4-methylbenzophenone, 4,4'-bis(diethylamino) benzophenone, methyl o-benzoylbenzoate, 4- Phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) benzophenone, or 2,4,6-trimethylbenzophenone. ; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl methyl ketal; Acetophenone compounds, such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, or 1-hydroxycyclohexyl phenyl ketone; Anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, or 2-amylanthraquinone; Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, or 2,4-diisopropylthioxanthone; Alkylphenone compounds such as acetophenone dimethyl ketal; triazine compounds; biimidazole compounds; Acylphosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compound; hydroxyketone compounds; and aminobenzoate compounds. As a photopolymerization initiator, these compounds can be used alone or in a mixture of two or more thereof.

The curable resin composition may contain one or more additives, such as antistatic agents, surfactants, leveling agents, thixotropy-imparting agents, anti-fouling agents, printability improvers, antioxidants, weathering stabilizers, light-fastening stabilizers, ultraviolet absorbers, heat stabilizers, colorants. , and fillers, if desired.

The curable resin composition may contain solvents as desired to dilute it to a concentration that allows for easy molding. The solvent is not particularly limited as long as the solvent does not react with the components of the curable resin composition and any other components or catalyze (promote) self-reaction (including decomposition reactions) of these components. Examples of solvents include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone.

The curable resin composition can be obtained by mixing and stirring these components.

2. Hard court

In the molded body of the present invention, part or all of the surface of the substrate is covered with a hard coat. The hard coat is responsible for improving the surface hardness of the molded body of the invention and preferably improves its wear resistance. The hard coat can have high transparency from a designability standpoint. Preferably, the hard coat itself is uncolored so that it can be easily colored to a desired color from the standpoint of design characteristics. Part or all of the surface of the substrate may be covered with a hard coat depending on the shape, application and purpose of the molded body of the present invention.

The hard coat includes a first hard coat layer and a second hard coat layer from the surface layer side.

As used herein, “surface layer side” means the side that is close to the outer side (e.g., the outer side of a household appliance) when an article comprising a molded body with the first and second hard coat layers is used in the field. Additionally, herein, placing one layer on the “surface layer side” of another layer includes those layers being in direct contact with each other, with another single layer or a plurality of other layers intervening therebetween. do.

2-1. 1st hard court

The first hard coat is formed from a paint containing no inorganic particles. The first hard coat preferably includes (A) 100 parts by mass of a polyfunctional (meth)acrylate, (B) 0.01 to 7 parts by mass of a water repellent, and (C) 0.01 to 10 parts by mass of a silane coupling agent, and the inorganic particles It is formed from a paint that does not contain.

The first hard coat usually forms the surface of the molded body of the present invention. When an article is made using the molded body of the present invention, the first hard coat typically forms the surface of the article. The first hard coat preferably exhibits good abrasion resistance and maintains surface characteristics such as water repellency even after repeated wiping with a handkerchief or the like.

Inorganic particles (e.g. silica (silicon dioxide); aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, cerium oxide , metal oxide particles formed of magnesium fluoride, sodium fluoride, etc.; metal sulfide particles; metal nitride particles; and metal particles) are very effective in improving the hardness of the hard coat. . On the other hand, the interaction between the inorganic particles and the resin component, such as the polyfunctional (meth)acrylate of component (A), is weak, resulting in insufficient wear resistance. Accordingly, the present invention generally provides that the first hard coat forming the outermost surface does not contain inorganic particles to maintain wear resistance, and the second hard coat preferably contains average particles of 1 to 300 nm to improve hardness. By containing a certain amount of inorganic particles with a certain size, the above problem was solved.

Here, “free from” inorganic particles means not containing a significant amount of inorganic particles. In the field of hard coat forming coatings, a significant amount of inorganic particles is usually about 1 part by mass or more per 100 parts by mass of the polyfunctional (meth)acrylate of component (A). Therefore, “not containing” inorganic particles can be rephrased as follows. That is, the amount of the inorganic particles is usually 0 part by mass or more and usually less than 1 part by mass, preferably 0.1 part by mass or less, more preferably 0.01 part by mass or less, with respect to 100 parts by mass of component (A).

(A) Multifunctional (meth)acrylate

The polyfunctional (meth)acrylate of component (A) is a (meth)acrylate having two or more (meth)acryloyl groups in one molecule. The component has two or more (meth)acryloyl groups in one molecule and thus acts to form a hard coat through polymerization and curing with active energy rays such as ultraviolet rays or electron beams.

Examples of polyfunctional (meth)acrylates include (meth)acryloyl group-containing difunctional reactive monomers such as diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6- Hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2,2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl) propane, or 2,2'-bis(4- (meth)acryloyloxypolypropyleneoxyphenyl) propane; (meth)acryloyl group-containing trifunctional reactive monomers, such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, or pentaerythritol tri(meth)acrylate; (meth)acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra(meth)acrylate; (meth)acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth)acryloyl group-containing octafunctional reactive monomers such as tripentaerythritol acrylate; and polymers (oligomers and prepolymers) containing one or more types thereof as constituent monomers. As component (A) polyfunctional (meth)acrylate, these compounds can be used alone or in a mixture of two or more thereof. Here, the term (meth)acrylate means acrylate or methacrylate.

(B) Water repellent

The water repellent agent of component (B) is responsible for improving water repellency.

Examples of water repellent agents include wax water repellent agents such as paraffin wax, polyethylene wax, or acrylate-ethylene copolymer wax; Silicone water repellent agents such as silicon oil, silicon resin, polydimethylsiloxane, or alkylalkoxysilane; and fluorine-containing water repellent agents, such as fluoropolyether water repellent or fluoropolyalkyl water repellent. As the water repellent of component (B), these compounds can be used alone or in a mixture of two or more thereof.

Among these compounds, the fluoropolyether water repellent is preferred as the water repellent for component (B) from the viewpoint of water repellency. A water repellent containing a compound having a (meth)acryloyl group and a fluoropolyether group in the molecule (hereinafter abbreviated as (meth)acryloyl group-containing fluoropolyether water repellent) is, component (A) It is further used as a water repellent for component (B) from the viewpoint of preventing problems such as bleed-out of component (B) due to chemical bonds or strong interactions between the polyfunctional (meth)acrylate and component (B). desirable. In order for a blend of an acryloyl group-containing fluoropolyether water repellent and a methacryloyl group-containing fluoropolyether water repellent to exhibit good water repellency while maintaining high transparency, the polyfunctionality (meth) of component (A) is added. From the viewpoint of appropriately controlling the chemical bond or interaction between the acrylate and the water repellent of component (B), it is even more preferable as the water repellent of component (B).

It should be noted that the (meth)acryloyl group-containing fluoropolyether water repellent is clearly distinct from component (A) in that it contains fluoropolyether groups in the molecule. Here, the compound having two or more (meth)acryloyl groups and fluoropolyether groups in one molecule is a (meth)acryloyl group-containing fluoropolyether water repellent, which is component (B). That is, compounds having fluoropolyether groups are excluded from the definition of polyfunctional (meth)acrylate of component (A).

From the viewpoint of preventing problems such as bleed-out of component (B), the amount of the water repellent of component (B) is usually 7 parts by mass or less per 100 parts by mass of the polyfunctional (meth)acrylate of component (A), preferably 7 parts by mass or less. It is preferably 4 parts by mass or less, more preferably 2 parts by mass or less. At the same time, the compounding amount of the water repellent of component (B) is usually 0.01 part by mass or more, preferably 0.05 part by mass or more, and more preferably 0.1 part by mass or more from the viewpoint of obtaining the effect of using the water repellent of component (B). The mixing amount of the water repellent is usually 0.01 parts by mass or more and 7 parts by mass or less, preferably 0.01 parts by mass or more and 4 parts by mass or less, or 0.01 parts by mass or more, based on 100 parts by mass of the polyfunctional (meth)acrylate of component (A). to 2 parts by mass or less, preferably 0.05 to 7 parts by mass, 0.05 to 4 parts by mass, or 0.05 to 2 parts by mass, or preferably 0.1 to 7 parts by mass. It may be less than or equal to 0.1 parts by mass and less than or equal to 4 parts by mass, or greater than or equal to 0.1 parts by mass and less than or equal to 2 parts by mass.

(C) Silane coupling agent

Component (C) serves to improve the adhesion between the first hard coat and the second hard coat.

Silane coupling agents include hydrolyzable groups (e.g., alkoxy groups, such as methoxy groups or ethoxy groups; acyloxy groups, such as acetoxy groups; or halogen groups, such as chloro groups) and organic functional groups (e.g., amino groups). , mercapto group, vinyl group, epoxy group, methacryloxy group, acryloxy group, or isocyanate group). Among these compounds, the silane coupling agent having an amino group (i.e., a silane compound having an amino group and a hydrolyzable group) and the silane coupling agent having a mercapto group (i.e., a silane compound having a mercapto group and a hydrolyzable group) are: It is preferred as the silane coupling agent of component (C). A silane coupling agent having an amino group is more preferable from the viewpoint of adhesiveness and odor.

Examples of silane coupling agents having an amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-( Aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene ) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane.

Examples of silane coupling agents with mercapto groups include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

As the silane coupling agent of component (C), these compounds can be used alone or in a mixture of two or more thereof.

From the viewpoint of ensuring the adhesion-improving effect, the amount of the silane coupling agent of component (C) is preferably 0.01 parts by mass or more, based on 100 parts by mass of the polyfunctional (meth)acrylate of component (A). Preferably it is 0.05 parts by mass or more, more preferably 0.1 parts by mass or more. At the same time, the compounding amount of the silane coupling agent of component (C) may be usually 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 1 part by mass or less from the viewpoint of the pot life of the paint. The compounding amount of the silane coupling agent is usually 0.01 parts by mass or more and 10 parts by mass or less, preferably 0.01 parts by mass or more and 5 parts by mass or less, or 0.01 parts by mass, based on 100 parts by mass of the polyfunctional (meth)acrylate of component (A). at least 0.05 parts by mass and at most 1 part by mass, preferably at least 0.05 parts by mass and at most 10 parts by mass, at least 0.05 parts by mass and at most 5 parts by mass, or at least 0.05 parts by mass and at most 1 part by mass, or preferably at least 0.1 parts by mass. It may be more than 10 parts by mass or less, 0.1 parts by mass or more and 5 parts by mass or less, or 0.1 parts by mass or more and 1 part by mass or less.

Note that the blended amount of the silane coupling agent of component (C) within any of the conventional or preferred ranges mentioned herein may be combined with the blended amount of the water repellent agent of component (B) within any of the conventional or preferred ranges mentioned above. do.

(F) Resin fine particles having an average particle size of 0.5 to 10 μm

When imparting anti-glare properties to the molded body of the present invention, the first hard coat forming paint may further include (F) resin fine particles having an average particle size of 0.5 to 10 μm. The resin fine particles of component (F) may strongly interact with resin components such as polyfunctional (meth)acrylate of component (A).

Examples of resin fine particles include resin fine particles of silicon-based resin (silicone resin), styrene resin, acrylic resin, fluororesin, polycarbonate resin, ethylene resin, and cured resin of amino compounds and formaldehyde. Among these compounds, fine particles of silicon-based resin, acrylic resin, and fluororesin are preferred in terms of low specific gravity, lubricity, dispersibility, and solvent resistance. True spherical particles are preferred from the viewpoint of improving light diffusion. As resin fine particles, these compounds can be used alone or in a mixture of two or more types thereof. The resin fine particles may be at least one selected from the group consisting of silicon-based resin fine particles, acrylic resin fine particles, and fluororesin fine particles. Additionally, the resin fine particles may be at least one selected from the group consisting of silicon-based resin fine particles and acrylic resin fine particles.

The average particle size of the resin fine particles of component (F) may usually be 0.5 μm or more, preferably 1 μm or more, from the viewpoint of reliably obtaining anti-glare properties. On the other hand, when it is intended to maintain the transparency of the hard coat, the average particle size of the resin fine particles of component (F) may usually be 10 μm or less, preferably 6 μm or less. The average particle size of the resin fine particles of component (F) may be usually 0.5 μm or more and 10 μm or less, preferably 0.5 μm or more and 6 μm or less, 1 μm or more and 10 μm or less, or 1 μm or more and 6 μm or less. .

Incidentally, here, the average particle size of the resin fine particles is the particle size distribution in which accumulation from the small side of the particle size is measured using a laser diffraction/scattering particle size analyzer "MT3200II" (trade name) manufactured by [Nikkiso Co., Ltd]. This is the particle size that is 50% by mass in the curve.

The resin fine particles of component (F) are preferably spherical, more preferably truly spherical from the viewpoint of improving light diffusivity. The fact that the resin fine particles of component (F) are truly spherical means that the sphericity of the particles may preferably be 0.90 or more, more preferably 0.95 or more. Sphericity is a measure of how spherical a particle is. Sphericity as referred to herein is obtained by dividing the surface area of a sphere having the same volume as the particle by the surface area of the particle, and can be expressed as ψ = (6Vp) ^2/3 π ^1/3 /Ap. At this time, Vp represents the particle volume, and Ap represents the particle surface area. Sphericity is 1 for spherical particles.

The blended amount of the resin fine particles of component (F) varies depending on the level of anti-glare properties to be imparted, but is usually 0.01 to 15 parts by mass, preferably 100 parts by mass of the polyfunctional (meth)acrylate of component (A). It may be 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and even more preferably 0.3 to 3 parts by mass. The blending amount of the resin fine particles of component (F) may preferably be 0.5 to 3 parts by mass from the viewpoint of wear resistance. According to another aspect, the blending amount of the resin fine particles of component (F) is preferably 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.01 to 3 parts by mass, 0.1 to 100 parts by mass of component (A). 15 parts by mass, 0.1 to 5 parts by mass, 0.1 to 3 parts by mass, 0.2 to 15 parts by mass, 0.2 to 10 parts by mass, 0.2 to 3 parts by mass, 0.3 to 15 parts by mass, 0.3 to 10 parts by mass, 0.3 to 5 parts by mass parts, 0.5 to 15 parts by mass, 0.5 to 10 parts by mass, or 0.5 to 5 parts by mass.

The first hard coat forming paint preferably further comprises a compound having two or more isocyanate groups (-N=C=O) in one molecule and/or a photopolymerization initiator from the viewpoint of improving curability with active energy rays. Includes.

Examples of compounds having two or more isocyanate groups in one molecule include methylenebis-4-cyclohexylisocyanate; Polyisocyanates, such as the trimethylolpropane adduct form of tolylene diisocyanate, the trimethylolpropane adduct form of hexamethylene diisocyanate, the trimethylolpropane adduct form of isophorone diisocyanate, the isocyanurate form of tolylene diisocyanate. , the isocyanurate form of hexamethylene diisocyanate, the isocyanurate form of isophorone diisocyanate, or the biuret form of hexamethylene diisocyanate; and urethane crosslinkers such as blocked isocyanates of polyisocyanates. As a compound having two or more isocyanate groups in one molecule, these compounds can be used alone or in a mixture of two or more types thereof. In crosslinking, catalysts such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added if necessary.

Examples of photopolymerization initiators are benzophenone compounds such as benzophenone, methyl-o-benzoyl benzoate, 4-methylbenzophenone, 4,4'-bis(diethylamino) benzophenone, methyl o-benzoylbenzoate, 4- Phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) benzophenone, or 2,4,6-trimethylbenzophenone. ; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl methyl ketal; Acetophenone compounds, such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, or 1-hydroxycyclohexyl phenyl ketone; Anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, or 2-amylanthraquinone; Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, or 2,4-diisopropylthioxanthone; Alkylphenone compounds such as acetophenone dimethyl ketal; triazine compounds; biimidazole compounds; Acylphosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compound; hydroxyketone compounds; and aminobenzoate compounds. As a photopolymerization initiator, these compounds can be used alone or in a mixture of two or more thereof.

The first hard coat forming paint may, if desired, contain one or more additives, such as antistatic agents, surfactants, leveling agents, thixotropy-imparting agents, anti-fouling agents, printability improvers, antioxidants, weathering stabilizers, lightfastness stabilizers, ultraviolet absorbers, It may include heat stabilizers, organic particulates, and organic colorants.

The first hard coat forming paint may contain a solvent as desired to dilute it to a concentration that allows for easy application. The solvent is not particularly limited, provided that the solvent does not react with any of components (A) to (C) and any other components, or catalyzes (promotes) self-reactions (including decomposition reactions) of these components. . Examples of solvents include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As solvents, these compounds can be used alone or in mixtures of two or more thereof.

The first hard coat forming paint can be obtained by mixing and stirring these components.

The method of forming the first hard coat using the first hard coat forming paint is not particularly limited, but known application methods can be used. Examples of the application methods include dip coating, spray coating, spin coating, and air knife coating. Application is not limited to once, but may be repeated two or more times. Moreover, when the hard coat forming portion of the molded body of the present invention is flat, methods such as roll coating, gravure coating, reverse coating, or die coating can be applied. there is.

The thickness of the first hard coat is preferably 0.5 μm or more, more preferably 1 μm or more from the viewpoint of wear resistance and hardness. At the same time, the thickness of the first hard coat is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less from the viewpoint of hardness and adhesion to the second hard coat. The thickness of the first hard coat is preferably 0.5 μm or more and 5 μm or less, more preferably 0.5 μm or more and 4 μm or less, 0.5 μm or more and 3 μm or less, 1 μm or more and 5 μm or less, 1 μm or more. It may be 4 μm or less, or 1 μm or more to 3 μm or less.

2-2. 2nd hard court

The second hard coat is formed from a paint containing inorganic particles. The second hard coat preferably consists of (A) 100 parts by mass of a polyfunctional (meth)acrylate; and (E) 50 to 300 parts by mass of inorganic fine particles having an average particle size of 1 to 300 nm.

(A) The multifunctional (meth)acrylate is as described above in the description of the first hard coat forming paint. As component (A), these compounds can be used alone or in mixtures of two or more thereof.

(D) Inorganic fine particles with an average particle size of 1 to 300 nm

The inorganic fine particles of component (D) play a role in significantly improving the surface hardness of the molded body of the present invention.

Examples of inorganic particulates include silica (silicon dioxide); metal oxide fine particles formed of aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, cerium oxide, etc.; metal fluoride particles formed of magnesium fluoride, sodium fluoride, etc.; metal sulfide particulates; metal nitride particulates; and metal particulates.

Among these compounds, in order to obtain a hard coat with higher surface hardness, fine particles formed of silica or aluminum oxide are preferred, and fine particles formed of silica are more preferred. Examples of commercially available silica fine particles include Snowtex (trade name) from Nissan Chemical Industries, Ltd. and Quartron (trade name) from Fuso Chemical Co., Ltd..

To improve the dispersibility of inorganic fine particles in the paint or to improve the surface hardness of the obtained hard coat, a silane coupling agent such as vinylsilane or aminosilane; Titanate coupling agent; Aluminate coupling agent; Organic compounds having reactive functional groups, such as ethylenically unsaturated bonding groups, such as (meth)acryloyl groups, vinyl groups, or allyl groups, or epoxy groups; Surface-treating agents such as fatty acids or fatty acid metal salts; It is preferable to use inorganic fine particles applied for surface treatment such as.

As the inorganic fine particles of component (D), these compounds can be used alone or in a mixture of two or more thereof.

The average particle size of the inorganic fine particles of component (D) is 300 nm or less, preferably 200 nm or less, more preferably 120 nm or less, from the viewpoint of reliably obtaining the hardness-improving effect of the hard coat. Meanwhile, the lower limit of the average particle size is not specifically specified, but the average particle size of commonly available inorganic fine particles is at most about 1 nm.

Incidentally, here, the average particle size of the inorganic fine particles is the particle size distribution in which accumulation from the small side of the particle size is measured using a laser diffraction/scattering particle size analyzer "MT3200II" (trade name) manufactured by [Nikkiso Co., Ltd]. This is the particle size that is 50% by mass in the curve.

From the viewpoint of surface hardness, the blending amount of the inorganic fine particles of component (D) is usually 50 parts by mass or more, preferably 80 parts by mass or more with respect to 100 parts by mass of the polyfunctional (meth)acrylate of component (A). At the same time, the blending amount of the inorganic fine particles of component (D) is usually 300 parts by mass or less, preferably 200 parts by mass or less, and more preferably 160 parts by mass or less from the viewpoint of transparency. The blending amount of the inorganic fine particles is usually 50 parts by mass or more and 300 parts by mass or less, preferably 50 parts by mass or more and 200 parts by mass or less, or 50 parts by mass or more, based on 100 parts by mass of the polyfunctional (meth)acrylate of component (A). It may be from 80 parts by mass to 160 parts by mass or less, or preferably from 80 parts by mass to 300 parts by mass, from 80 parts by mass to 200 parts by mass, or from 80 parts by mass to 160 parts by mass.

(E) Leveling agent

The second hard coat forming paint preferably further comprises (E) a leveling agent from the viewpoint of improving the second hard coat surface so that the first hard coat can be easily formed.

Examples of the leveling agent (E) of the component include acrylic leveling agent, silicone leveling agent, fluorine leveling agent, silicone-acrylate copolymer leveling agent, fluorine-modified acrylic leveling agent, fluorine-modified silicone leveling agent, and functional groups (e.g. For example, alkoxy groups such as methoxy groups or ethoxy groups, acyloxy groups, halogen groups, amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, or isocyanate groups) are introduced. . Among these compounds, a silicone-acrylate copolymer leveling agent is preferred as the leveling agent for component (E). As the leveling agent of component (E), these compounds can be used alone or in a mixture of two or more thereof.

The compounding amount of the leveling agent of component (E) is, with respect to 100 parts by mass of the polyfunctional (meth)acrylate of component (A), from the viewpoint of smoothing the surface of the second hard coat so that the first hard coat can be easily formed, It is usually 0.01 part by mass or more, preferably 0.1 part by mass or more, and more preferably 0.2 part by mass or more. At the same time, the compounding amount of the leveling agent of component (E) is usually 1 part by mass or less, preferably 0.6 part by mass or less, more preferably 1 part by mass or less, from the viewpoint of satisfactorily applying the first hard coat forming paint to the second hard coat without backlash. In other words, it may be 0.4 parts by mass or less. The blending amount of the leveling agent is usually 0.01 part by mass or more and 1 part by mass or less, preferably 0.01 part by mass or more and 0.6 part by mass or less, or 0.01 part by mass, based on 100 parts by mass of the polyfunctional (meth)acrylate of component (A). Part by mass or more and 0.4 parts by mass or less, preferably 0.1 or more parts by mass and 1 part by mass or less, 0.1 or more parts by mass and 0.6 parts by mass or less, or 0.1 parts by mass or more and 0.4 parts by mass or less, or preferably 0.2 parts by mass. It may be more than 1 part by mass or less, 0.2 parts by mass or more and 0.6 parts by mass or less, or 0.2 parts by mass or more and 0.4 parts by mass or less.

that the blending amount of the leveling agent of component (E) in any of the conventional or preferred ranges mentioned herein can be combined with the blending amount of the inorganic fine particles of component (D) in any of the conventional or preferred ranges mentioned above. You must keep this in mind.

The second hard coat forming paint preferably further comprises a compound having two or more isocyanate groups (-N=C=O) in one molecule and/or a photopolymerization initiator from the viewpoint of improving curability of active energy rays. .

As the compound having two or more isocyanate groups in one molecule for the second hard coat, the same compounds as those described above for the first hard coat forming paint can be used. As a compound having two or more isocyanate groups in one molecule, these compounds can be used alone or in a mixture of two or more types thereof.

As a photopolymerization initiator for the second hard coat, the same compounds as those described above for the first hard coat forming paint can be used. As a photopolymerization initiator, these compounds can be used alone or in a mixture of two or more thereof.

The second hard coat forming paint may contain one or more additives, such as antistatic agents, surfactants, thixotropy-imparting agents, antifouling agents, printability improvers, antioxidants, weathering stabilizers, lightfastness stabilizers, ultraviolet absorbers, heat stabilizers, colorants. , and organic particulates, if desired.

The second hard coat forming paint may contain solvents as desired for dilution to a concentration that allows for easy application. The solvent is not particularly limited, as long as the solvent does not react with any of components (A) and (D) and any other components, or does not catalyze (accelerate) self-reactions (including decomposition reactions) of these components. No. Examples of solvents include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. Among these compounds, 1-methoxy-2-propanol is preferred. As solvents, these compounds can be used alone or in mixtures of two or more thereof.

The second hard coat forming paint can be obtained by mixing and stirring these components.

The method of forming the second hard coat using the second hard coat forming paint is not particularly limited, but known application methods can be used. Examples of the application methods include dip coating, spray coating, spin coating, and air knife coating. Application is not limited to once, but may be repeated two or more times. Moreover, when the hard coat forming portion of the molded body of the present invention is flat, methods such as roll coating, gravure coating, reverse coating, or die coating can be applied. there is.

From the viewpoint of surface hardness, the thickness of the second hard coat is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, and even more preferably 18 μm or more. At the same time, from the viewpoint of impact resistance, the thickness of the second hard coat may be preferably 30 μm or less, more preferably 27 μm or less, and even more preferably 25 μm or less. The thickness of the second hard coat is preferably 5 μm or more and 30 μm or less, more preferably 5 μm or more and 27 μm or less, 5 μm or more and 25 μm or less, 10 μm or more and 30 μm or less, and 10 μm or more. 27 ㎛ or less, 10 ㎛ or more to 25 ㎛ or less, 15 ㎛ or more to 30 ㎛ or less, 15 ㎛ or more to 27 ㎛ or less, 15 ㎛ or more to 25 ㎛ or less, 18 ㎛ or more to 30 ㎛ or less, 18 ㎛ or more to 27 ㎛ It may be less than or equal to 18 μm or more and less than or equal to 25 μm.

It should be noted that the thickness of the second hard coat in any of the preferred ranges mentioned herein may be combined with the thickness of the first hard coat in any of the preferred ranges mentioned above.

The molded body of the present invention may include any layer(s) other than the first hard coat, the second hard coat, and the substrate. Examples of optional layers include hard coats other than the first and second hard coats, resin layers other than the substrate, anchor coats, transparent conductive layers, high refractive index layers, low refractive index layers, and anti-reflection layers.

3. End face cutting-machining

The molded body of the present invention is subjected to cutting-processing of its end face, for example, so-called R-face cutting-machining (Figure 3(a)) or so-called C-face cutting-machining (Figure 3(b)), It may have a shape obtained by chamfering the end portion. An example of a method of manufacturing a shaped body having a shape whose ends are chamfered is to first subject the ends of a substrate to cutting-machining, and then form a second hard coat on the surface of the substrate whose ends have been subjected to cutting-machining. and then forming a first hard coat on the surface of the formed second hard coat; First form a second hard coat on the surface of the substrate, then subject the end of the resulting body to cutting-machining with the second hard coat, and then apply a first hard coat on the surface of the resulting cutting-machined body. How to form a; and a method of first forming a second hard coat on the surface of the substrate, then forming a first hard coat on the surface of the formed second hard coat, and then subjecting the resulting end portion of the formed body to cutting-machining. Includes. In an embodiment of the third method, after subjecting the end portion of the formed body to cut-machining, a coat can be further formed on the cut-machined surface using an optional paint, by methods such as dip coating. The first hard coat forming the surface of the molded body of the present invention usually has good water repellency. Therefore, it is easy to form a coat only on the cut-machined surface. That is, even if dip coating is performed using any paint without special masking after subjecting the end of the molded body to cut-machining, the coat can be expected to form only on the cut-machined surface. Examples of optional paints include, but are not limited to, the first hard coat forming paint and the second hard coat forming paint mentioned above.

4. Preferred physical properties of articles and molded bodies containing the molded body of the present invention

Articles containing the molded body of the present invention are not particularly limited, but examples thereof include housings of home appliances such as televisions, refrigerators, washing machines, vacuum cleaners, microwave ovens, or air conditioners; A front panel of a door that opens and closes the front part of the main body of an article such as a refrigerator, washing machine, dish rack, or clothes rack, and a flat panel of a lid that opens and closes the flat part of the main body; Housings for information electronic devices such as smartphones, tablet terminals, car navigation systems, digital cameras, or personal computers, and curved display faceplates; and instrument clusters and shift knobs of automobiles.

When the molded body of the present invention is used for applications requiring transparency, such as curved display faceplates such as smartphones, tablet terminals, car navigation systems, or personal computers, the total light transmittance of the molded body of the present invention (JIS K7361 -1:1997 (measured with a turbidity meter "NDH 2000" (trade name) manufactured by [Nippon Denshoku Industries Co., Ltd.]) is preferably at least 85%, more preferably at least 88%, even more preferably at least 85%. is 89% or more, most preferably 90% or more. Due to the total light transmittance of 85% or more, the molded body of the present invention can be suitably used as a curved display face plate, etc. The higher the total light transmittance, the more desirable.

In the molded body of the present invention, the first hard coat surface preferably has a pencil hardness of 5H or more, more preferably 6H or more, even more preferably 7H or more (according to JIS K5600-5-4, under the condition of a load of 750 g) (measured with pencil “UNI” (trade name) manufactured by [Mitsubishi Pencil Co., Ltd.]). The higher the pencil hardness, the more desirable it is.

The molded body of the present invention preferably has a total light transmittance of at least 85% and a pencil hardness of at least 5H on the first hard coat surface. Additionally, the molded body of the present invention preferably has a total light transmittance of at least 88% and a pencil hardness of at least 5H on the first hard coat surface, a total light transmittance of at least 89% and a pencil hardness of at least 5H on the first hard coat surface, and a first A total light transmittance of at least 90% and a pencil hardness of at least 5H on the hard court surface, a total light transmittance of at least 85% and a pencil hardness of at least 6H on the first hard court surface, a total light transmittance of at least 88% and a pencil hardness of at least 6H on the first hard court surface. Hardness, a total light transmittance of at least 89% and a pencil hardness of at least 6H on the first hard coat surface, a total light transmittance of at least 90% and a pencil hardness of at least 6H on the first hard coat surface, and a total light transmittance of at least 85% on the first hard coat surface. and a pencil hardness of at least 7H, a total light transmittance of at least 88% on the first hard coat surface and a pencil hardness of at least 7H, a total light transmittance of at least 89% on the first hard coat surface and a pencil hardness of at least 7H, or 90% on the first hard coat surface. It has a total light transmittance of % or more and a pencil hardness of 7H or more.

In the molded body of the present invention, the first hard coat surface preferably has a water contact angle of 100° or more, more preferably 105° or more. Due to the water contact angle of 100° or more on the first hard coat surface, the water repellency, fingerprint resistance, and anti-contamination properties of the molded body can be improved. The upper limit of the water contact angle is not specifically specified, but approximately 120° is usually sufficient. Here, the water contact angle is the value measured according to test (iii) in the examples described below.

In the molded body of the present invention, the water contact angle at the first hard coat surface after 20,000 reciprocating wipes with cotton is at least 100°. More preferably, the water contact angle after 25,000 reciprocating wipes on cotton is at least 100°. Due to the water contact angle of more than 100° after 20,000 reciprocating wipes with cotton, the surface characteristics such as water repellency, fingerprint resistance, or stain resistance of the molded body can be maintained even after repeated wipes with a handkerchief or the like. With respect to the number of wipes to the surface during which a water contact angle of 100° or more can be maintained, the greater the number, the more desirable. Here, the water contact angle after wiping onto cotton is the value measured according to test (iv) in the examples described below.

In the molded body of the present invention, preferably, the water contact angle at the first hard coat surface is at least 100°, and the water contact angle at the first hard coat surface after 20,000 reciprocating wipes with cotton is at least 100°. Moreover, in the molded body of the present invention, preferably, the water contact angle on the first hard coat surface is 105° or more, and the water contact angle on the first hard coat surface after 20,000 reciprocating wipes to the cotton is 100° or more, The water contact angle on the first hard court surface is greater than or equal to 100°, and the water contact angle on the first hard coat surface is greater than or equal to 100° after 25,000 reciprocating wipes with cotton, or the water contact angle on the first hard court surface is greater than or equal to 105°. ° or more, and the water contact angle on the first hard coat surface after 25,000 reciprocating wipes with cotton is more than 100°.

The total light transmittance in any of the preferred ranges mentioned above may be combined with the pencil hardness on the first hard coat surface in any of the preferred ranges mentioned above, and the water contact angle on the first hard coat surface mentioned herein and It should be noted that the water contact angle at the first hard coat surface after 20,000 reciprocating wipes or 25,000 reciprocating wipes to the surface mentioned herein may be combined and/or combined.

[Example]

Hereinafter, the present invention will be explained with reference to examples, but the present invention is not limited thereto.

Measurement and evaluation methods

In each of the following tests (i) to (ix), unless otherwise specified, a test piece was cut from the flat portion of the top of the molded body, and its physical properties were measured and evaluated.

(i) Total light transmittance

The total light transmittance of the test piece was measured according to JIS K7361-1:1997 using a turbidity meter "NDH2000" (trade name) manufactured by [Nippon Denshoku Industries Co., Ltd.].

(ii) Pencil hardness

The pencil hardness on the first hard coat surface of the molded body was measured according to JIS K5600-5-4 using a pencil “UNI” (trade name) manufactured by [Mitsubishi Pencil Co., Ltd] under the condition of a load of 750 g.

(iii) Water contact angle (initial water contact angle)

The water contact angle on the first hard coating surface of the molded body was calculated according to the method for calculating the water contact angle from the width and height of the water droplet (reference JIS R3257:1999) using an automatic contact angle meter "DSA20" (trade name) manufactured by [KRUSS GmbH]. It was measured by.

(iv) Abrasion resistance 1 (water contact angle after wiping to cotton)

A test piece measuring 150 mm in length and 50 mm in width was taken from the upper flat part of the molded body. The test piece was placed on a Gakushin tester according to JIS L0849:2013 with its first hard coat on the front side. Four stainless steel plates (10 mm long, 10 mm wide, 1 mm thick) covered with overlapping gauze (medical type 1 gauze from [Kawamoto Corp.]) were placed so that the length I width surface of the stainless steel plate was in contact with the test specimen. , was attached to the friction terminal of the Gakushin tester. A load of 350 g was placed on a stainless steel plate covered with gauze. The first hard coating surface of the test piece was rubbed with 10,000 reciprocations under the conditions of a travel distance of the friction terminal of 60 mm and a speed of 1 reciprocation/sec. Afterwards, the water contact angle of the cotton-wiped portion was measured according to the method of (iii). If the water contact angle was more than 100°, an additional 5,000 reciprocating rubbing was performed and the operation of measuring the water contact angle of the cotton-wiped part was repeated according to the method in (iii), and evaluation was performed according to the following categories. did.

A: The water contact angle was more than 100° even after 25,000 reciprocating rubbings.

B: The water contact angle was more than 100° after 20,000 reciprocating rubbings, but the water contact angle was less than 100° after 25,000 reciprocating rubbings.

C: The water contact angle was more than 100° after 15,000 reciprocating rubbings, but the water contact angle was less than 100° after 20,000 reciprocating rubbings.

D: The water contact angle was more than 100° after 10,000 reciprocating rubbings, but the water contact angle was less than 100° after 15,000 reciprocating rubbings.

E: The water contact angle was less than 100° after 10,000 reciprocating rubbings.

(v) Abrasion resistance 2 (steel wool resistance)

A test piece taken from the upper flat part of the molded body was placed on a Gakushin testing machine according to JIS L0849:2013 with its first hard coat on the front side. Next, #0000 steel wool was attached to the friction terminal of the Gakushin tester, and then a load of 500 g was applied. The surface of the test piece was rubbed back and forth 100 times, and then the rubbed area was visually observed. In cases where scratches were not observed, an additional round-trip rubbing was performed 100 times, the subsequent visual observation of the rubbed area was repeated, and evaluation was performed according to the following categories.

A: No scratches were observed, even after 500 reciprocating rubbings.

B: Scratches were not observed after 400 reciprocating rubbings, but scratches could be observed after 500 reciprocating rubbings.

C: Scratches were not observed after 300 reciprocating rubbings, but scratches could be observed after 400 reciprocating rubbings.

D: Scratches were not observed after 200 reciprocating rubbings, but scratches could be observed after 300 reciprocating rubbings.

E: No scratches were observed after 100 reciprocating rubbings, but scratches could be observed after 200 reciprocating rubbings.

F: Scratches could be observed after 100 reciprocating rubbings.

(vi) Square lattice pattern test (adhesion)

According to JIS K5600-5-6:1999, a square lattice pattern cut consisting of 100 cells (1 cell = 1 mm x 1 mm) was formed on the molded body from the first hard coat surface side. Afterwards, the tape for the adhesion test was pasted on the square grid pattern, rubbed with a finger, and then peeled off. The evaluation categories were in accordance with Table 1 in the above standards of JIS.

Category 0: The edges of the cut were completely smooth and none of the squares of the grid were delaminated.

Category 1: Small delamination of the coat was observed at the intersection of the cuts. Apparently less than 5% of the cross-cutting area was affected.

Category 2: Coat was delaminated along edges and/or at the intersection of cuts. Clearly more than 5% but less than 15% of the cross-cutting area was affected.

Category 3: The coat was partially or fully delaminated along the edges of the cut, and/or various parts of the spinning were partially or fully delaminated. Apparently more than 15% but less than 35% of the cross-cutting area was affected.

Class 4: The coat was partially or completely significantly delaminated along the edge of the cut, and/or some portions of the spinning were partially or completely delaminated. Clearly more than 35% but less than 65% of the cross-cutting area was affected.

Category 5: When the degree of delamination is greater than that in Category 4.

(vii) Weather resistance

Sunlight carbon arc described in JIS B7753:2007 under the conditions in Table 10 of JIS A5759:2008 (test specimens obtained from molded bodies with sizes of 125 mm in length and 50 mm in width were used as is, and the test specimens were not attached to glass). A 300 hour accelerated weathering test was performed using a lamp type weathering tester. The number of tests N was 3. In all tests, cases where there was no change in appearance such as swelling, cracking, or peeling in the test specimen were evaluated as acceptable products (indicated by ◎ in the table), and other cases were evaluated as unacceptable products (indicated by × in the table). evaluated.

(viii) Haze

The haze of the test piece was measured according to JIS K7136:2000 using a turbidity meter "NDH2000" (trade name) manufactured by [Nippon Denshoku Industries Co., Ltd.].

(ix) Y value of XYZ colorimetric system based on 2-degree field of view

Using the spectrophotometer "SolidSpec-3700" (trade name) and reflection unit "Absolute reflectance measurement device incident angle 5°" (trade name) from [Shimadzu Corporation], 5° mirror reflection (place the reflection unit on the integrating sphere) according to the manual of the spectrophotometer. The Y value of the XYZ colorimetric system of the test piece was measured under the conditions of (placed in front).

raw materials used

(A) Multifunctional (meth)acrylate

(A-1) Dipentaerythritol hexaacrylate (hexafunctional)

(A-2) Pentaerythritol triacrylate (trifunctional)

(B) Water repellent

(B-1) Acryloyl group-containing fluoropolyether water repellent "KY-1203" (trade name) from [Shin-Etsu Chemical Co., Ltd.]: solid content 20 mass%

(B-2) Methacryloyl group-containing fluoropolyether water repellent “FOMBLIN MT70” (trade name) from [Solvay S.A.]: solid content 70 mass%

(C) Silane coupling agent

(C-1) N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane “KBM-602” (trade name) manufactured by [Shin-Etsu Chemical Co., Ltd.]

(C-2) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane “KBM-603” (trade name) manufactured by [Shin-Etsu Chemical Co., Ltd.]

(C-3) 3-Aminopropyltrimethoxysilane “KBM-903” (trade name) manufactured by [Shin-Etsu Chemical Co., Ltd.]

(C-4) 3-Mercaptopropylmethyldimethoxysilane “KBM-802” (trade name) manufactured by [Shin-Etsu Chemical Co., Ltd.]

(C-5) 3-Glycidoxypropyltrimethoxysilane “KBM-403” (trade name) manufactured by [Shin-Etsu Chemical Co., Ltd.]

(D) Inorganic fine particles with an average particle size of 1 to 300 nm

(D-1) Silica fine particles with an average particle size of 20 nm, applied to surface treatment with a silane coupling agent having a vinyl group

(E) Leveling agent

(E-1) Silicone-acrylate copolymer leveling agent "DISPARLON NSH-8430HF" (trade name) from [Kusumoto Chemicals, Ltd.]: solid content 10 mass%

(E-2) Silicone-acrylate copolymer leveling agent "BYK-3550" (trade name) from [BYK Japan KK]: solid content 52 mass%

(E-3) Acrylic polymer leveling agent “BYK-399” (trade name) from [BYK Japan KK]: solid content 100 mass%

(E-4) Silicone leveling agent “DISPARLON LS-480” (trade name) from [Kusumoto Chemicals, Ltd.]: solid content 100 mass%

(F) Resin fine particles having an average particle size of 0.5 to 10 μm

(F-1) True spherical silicone resin microparticles “Tospearl 120” (trade name) from [Momentive Performance Materials Corporation]: average particle size 2 μm.

(F-2) True spherical silicone resin microparticles “Tospearl 130” (trade name) from [Momentive Performance Materials Corporation]: average particle size 3 μm.

(F-3) Acrylic resin fine particles “MA-180TA” (trade name) from [Soken Chemical & Engineering Co., Ltd.]: average particle size 1.8 μm

(F-4) Acrylic resin fine particles “MX-80H3wT” (trade name) from [Soken Chemical & Engineering Co., Ltd.]: average particle size 0.5 μm

(F-5) Acrylic resin fine particles “FH-S010” (trade name) manufactured by [Toyobo Co., Ltd.]: average particle size 10 μm.

(G) Random component

(G-1) Phenyl ketone photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) “SB-PI714” (trade name) from [Shuang Bang Industrial Corp.]

(G-2) 1-methoxy-2-propanol

(H1) First hard coat forming paint

(H1-1) The paint is 100 parts by mass of (A-1), 2 parts by mass (0.40 parts by mass by mass of solid content) of (B-1), and 0.06 parts by mass (0.042 parts by mass by solid content) of (B-2). ), 0.5 parts by mass of (C-1), 4 parts by mass of (F-1), and 100 parts by mass of (F-2) were obtained by mixing and stirring. Table 1 is a table listing the ingredients and their mixing amounts. For (B-1) and (B-2), Table 1 shows the values in terms of solid content.

(H1-2 to H1-26) The first hard coat forming paint was obtained in a similar manner to (H1-1), except that the components and their mixing amounts were changed as shown in any one of Tables 1 to 3. did.

Table 1

Table 2

Table 3

(H2) Second hard coat forming paint

(H2-1) The paint is 100 parts by mass of (A-2), 140 parts by mass of (D-1), 2 parts by mass (0.2 parts by mass of solid content) of (E-1), and 17 parts by mass of (F-1). ), and 200 parts by mass of (F-2) were obtained by mixing and stirring. Table 4 is a table listing the ingredients and their mixing amounts. For (E-1), Table 4 shows the values in terms of solid content.

(H2-2 to H2-15) The second hard coat forming paint was obtained in a similar manner to (H2-1), except that the components and their mixing amounts were changed as shown in Table 4 or 5. For (E-2) as well as (E-1), Tables 4 or 5 also show the values in terms of solids content.

Table 4

Table 5

(a) Substrate

(a1-1) Substrate 1 formed by applying an acrylic resin sheet to vacuum forming

Using an apparatus equipped with an extruder and a T-die 12, a molten sheet (having a glass transition temperature of 119° C.) of acrylic resin “Optimas 6000” (trade name) manufactured by [Mitsubishi Gas Chemical Co., Ltd.] 11) is continuously extruded from the T-die 12, and a first mirror roll 13 rotating the molten sheet 11 (i.e. a roll for holding the molten sheet and sending the molten sheet to the subsequent conveying rolls, which is also (also applied) was supplied and introduced between the rotating second mirror roll 14 and pressed to obtain a transparent resin sheet with a thickness of 1 mm (see FIG. 4). As the set conditions at this time, the set temperature of the first mirror roll (13) was 120°C, the set temperature of the second mirror roll (14) was 110°C, and the resin temperature at the outlet of the T-die (12) was 300°C. . The obtained resin sheet had a total light transmittance of 92%, a haze of 0.5%, a yellowness of 0.3, and a tensile modulus of 3400 MPa. Then, using the obtained resin sheet, a substrate having the shape illustrated in Fig. 1 was formed as described above using a vacuum forming method. At this time, the pressure within space 9 was 1.0 × 10 ^-3 kPa. Figure 1(a) is a top view, and Figure 1(b) is a side view. In the substrate presented in Figure 1, the length of the major axis (1) at the top flat part with an oval shape was 20 cm, the length of the major axis (2) at the end with an oval shape was 30 cm, and the length of the major axis (2) at the end with an oval shape was 30 cm. The length of the minor axis at the flat part (3) was 10 cm, the length of the minor axis at the oval-shaped tip (4) was 20 cm, and the height from the tip to the upper part (5) was 5 cm.

(a1-2) Substrate 2 formed by applying an acrylic resin sheet to vacuum forming

Using an apparatus equipped with an extruder and a T-die 12, a melted sheet of poly(meth)acrylimide resin "PLEXIMID TT50" (trade name) from Evonik Industries AG (having a glass transition temperature of 154° C.) (11) is continuously extruded from the T-die (12), and the molten sheet (11) is fed and introduced between the rotating first mirror surface roll (13) and the rotating second mirror surface roll (14), and pressed to a thickness of 1 mm. A transparent resin sheet having a thickness was obtained (see Figure 4). As the set conditions at this time, the set temperature of the first mirror roll (13) was 140°C, the set temperature of the second mirror roll (14) was 120°C, and the resin temperature at the outlet of the T-die (12) was 300°C. . The obtained transparent resin sheet had a total light transmittance of 92%, a haze of 0.5%, a yellowness of 0.3, and a tensile modulus of elasticity of 4300 MPa. Then, using the obtained resin sheet, a substrate having the shape illustrated in Fig. 1 was formed as described above using a vacuum forming method. At this time, the pressure within space 9 was 1.0 × 10 ^-3 kPa.

(a2-1) Aromatic polycarbonate resin sheet

Using an apparatus equipped with an extruder and a T-die (12), a molten sheet of aromatic polycarbonate "CALIBRE 301-4" (trade name) from [Sumika Styron Polycarbonate Limited] (having a glass transition temperature of 151° C.) (11) is continuously extruded from the T-die (12), and the molten sheet is fed and introduced between the rotating first mirror surface roll (13) and the rotating second mirror surface roll (14) and pressed to a thickness of 1 mm. A transparent resin sheet was obtained (see Figure 4). As the set conditions at this time, the set temperature of the first mirror roll (13) was 140°C, the set temperature of the second mirror roll (14) was 120°C, and the resin temperature at the outlet of the T-die (12) was 300°C. . The obtained transparent resin sheet had a total light transmittance of 90%, a haze of 0.6%, a yellowness of 0.5, and a tensile modulus of elasticity of 2300 MPa. Then, using the obtained resin sheet, a substrate having the shape illustrated in Fig. 1 was formed as described above using a vacuum forming method. At this time, the pressure within space 9 was 1.0 × 10 ^-3 kPa.

(a3-1) Polyester resin sheet 1

Melting of an amorphous polyester resin (PETG resin) "Cadence GS1" (trade name) from Eastman Chemical Company (having a glass transition temperature of 81° C.) using an apparatus equipped with an extruder and a T-die (12). The sheet 11 is continuously extruded from the T-die 12, and the molten sheet 11 is fed and introduced between the rotating first mirror surface roll 13 and the rotating second mirror surface roll 14, and pressed to form 1 A transparent resin sheet with a thickness of mm was obtained (see Figure 4). As the set conditions at this time, the set temperature of the first mirror roll (13) was 80°C, the set temperature of the second mirror roll (14) was 40°C, and the resin temperature at the outlet of the T-die (12) was 200°C. . The obtained transparent resin sheet had a total light transmittance of 89%, a haze of 1.3%, a yellowness of 0.4, and a tensile modulus of elasticity of 1500 MPa. Then, using the obtained resin sheet, a substrate having the shape illustrated in Fig. 1 was formed as described above using a vacuum forming method. At this time, the pressure within space 9 was 1.0 × 10 ^-3 kPa.

(a3-2) Polyester resin sheet 2

Using an apparatus equipped with an extruder and a T-die (12), a molten sheet (11) of the amorphous polyester resin “Tritan FX200” (trade name) from Eastman Chemical Company (having a glass transition temperature of 119° C.) is continuously extruded from the T-die (12), and the molten sheet (11) is fed and introduced between the rotating first mirror surface roll (13) and the rotating second mirror surface roll (14), and pressed to obtain a thickness of 1 mm. A transparent resin sheet was obtained (see Figure 4). As the setting conditions at this time, the set temperature of the first mirror roll (13) was 80°C, the set temperature of the second mirror roll (14) was 40°C, and the resin temperature at the outlet of the T-die (12) was 230°C. . The obtained transparent resin sheet had a total light transmittance of 90%, a haze of 1.2%, a yellowness of 0.4, and a tensile modulus of elasticity of 1500 MPa. Then, using the obtained resin sheet, a substrate having the shape illustrated in Fig. 1 was formed as described above using a vacuum forming method. At this time, the pressure within space 9 was 1.0 × 10 ^-3 kPa.

(a4-1) Laminated sheet 1

Using a two-piece/three-layer multimanifold-type co-extrusion film forming device equipped with an extruder and a T-die, both outer layers were made of acrylic resin "Optimas 7500" (from Mitsubishi Gas Chemical Co., Ltd.) It was formed with aromatic polycarbonate "CALIBRE 301-4" (trade name) (having a glass transition temperature of 151°C) manufactured by [Sumika Styron Polycarbonate Limited] (having a glass transition temperature of 119°C). The melt-laminated sheet is continuously extruded from the T-die, the melt-laminated sheet is fed and introduced between the first rotating mirror roll and the second rotating mirror roll, and compressed to form a total thickness of 1 mm, with both outer layers of 0.1 mm. Transparent resin sheets each having a thickness of an intermediate layer of 0.8 mm were obtained. As the set conditions at this time, the set temperature of the first mirror roll was 120°C, the set temperature of the second mirror roll was 110°C, and the resin temperature at the outlet of the T-die was 300°C. The obtained transparent resin sheet had a total light transmittance of 91%, a haze of 0.6%, a yellowness of 0.5, and a tensile modulus of 2600 MPa. Then, using the obtained resin sheet, a substrate having the shape illustrated in Fig. 1 was formed as described above using a vacuum forming method. At this time, the pressure within space 9 was 1.0 × 10 ^-3 kPa.

(a5-1) Substrate formed by injection molding ABS/PC alloy resin

[Techno Polymer Co., Ltd.]'s ABS/PC alloy resin "Exceloy CK50" (trade name) was used in a 100 ton injection molding machine, with a cylinder temperature of 260℃, a die temperature of 70℃, and a molding speed of 250 mm/sec. By applying injection molding at an injection speed and holding pressure of 50 MPa, a thermoplastic resin substrate was obtained.

Example 1

The hard coat of (H2-1) was formed on the surface of the protruding surface of (a1-1) using a dip coating method to have a thickness of 22 μm after curing. Then, a hard coat of (H1-1) was formed on the surface of the formed hard coat using a dip coating method to have a thickness of 2 μm after curing. The obtained molded body was subjected to tests (i) to (ix). Table 6 shows the results. Here, “HC” in Table 6 and the following tables represents the abbreviation for hard coat.

Examples 2 to 16

A molded body was manufactured, and its physical properties were measured and evaluated in a manner similar to Example 1, except that the first hard coat forming paint shown in any one of Tables 6 to 8 was used instead of (H1-1). It was performed as follows. Tables 6 to 8 each show the results.

Examples 17 to 29

A molded body was manufactured, and its physical properties were measured and evaluated in a manner similar to Example 1, except that the second hard coat forming paint shown in any one of Tables 8 to 10 was used instead of (H2-1). It was performed as follows. Tables 8 to 10 each show the results.

Examples 30 to 34

A molded body was manufactured, and its physical properties were measured and evaluated in a similar manner to Example 1, except that the substrate shown in Table 10 was used instead of (a1-1). Table 10 shows the results.

Example 35

A molded body was manufactured, and its physical properties were measured and evaluated in a similar manner to Example 1, except that (a5-1), the substrate shown in Table 10, was used instead of (a1-1). Table 10 shows the results. (a5-1) is an opaque substrate, so tests (i) and (xiii) were omitted.

Examples 36 to 39

Molded bodies were prepared, and their physical properties were measured and evaluated in a similar manner to Example 1, except that the thickness of the first hard coat after curing changed as shown in Table 11. Table 11 shows the results.

Examples 40 to 43

Molded bodies were prepared, and their physical properties were measured and evaluated in a similar manner to Example 1, except that the thickness of the second hard coat after curing changed as shown in Table 11 or 12. Table 11 or 12 shows the results.

Examples 44 to 53

A molded body was prepared, and its physical properties were measured and evaluated in a similar manner to Example 1, except that the first hard coat forming paint shown in Table 12 or 13 was used instead of (H1-1). Table 12 or 13 shows the results.

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

Table 13

From these experimental results, it was found that the preferred molded body of the present invention had excellent surface hardness and excellent wear resistance. Additionally, preferred molded bodies of the present invention have good weather resistance and good adhesion to hard coats.

1 Length of the major axis at the upper flat part, which has an oval shape
2 Length of the major axis at the end having an oval shape
3 Length of the minor axis at the upper flat part, which has an oval shape
4 Length of minor axis at end with oval shape
5 Height from tip to top part
6 Resin sheet
7 infrared heater
8 forming die
9 Space between resin sheet (6) and forming die (8)
10 substrate
11 Molten resin sheet
12 T-Die
13 First mirror roll
14 Second mirror roll

Claims (20)

A molded body comprising a resin substrate as follows:
The substrate has a three-dimensional shape,
Part or all of the surface of the substrate is covered with a hard coat,
The hard coat includes, from the surface layer side, a first hard coat layer and a second hard coat layer,
The first hard court is:
(A) 100 parts by mass of polyfunctional (meth)acrylate;
(B) 0.01 to 7 parts by mass of a water repellent; and
(C) 0.01 to 10 parts by mass of a silane coupling agent
It is formed of a paint that contains and does not contain inorganic particles,
The second hard court is:
(A) 100 parts by mass of polyfunctional (meth)acrylate; and
(D) 50 to 300 parts by mass of inorganic fine particles having an average particle size of 1 to 300 nm.
A molded body formed from a paint containing a. The molded article according to claim 1, wherein (C) the silane coupling agent includes at least one selected from the group consisting of a silane coupling agent having an amino group and a silane coupling agent having a mercapto group. The molded article according to claim 1, wherein (B) the water repellent agent contains a (meth)acryloyl group-containing fluoropolyether water repellent agent. The molded article according to claim 1, wherein the second hard coat forming paint further comprises (E) 0.01 to 1 part by mass of a leveling agent. The molded article according to claim 4, wherein (E) the leveling agent includes a silicone-acrylate copolymer leveling agent. The molded article according to claim 1, wherein the first hard coat forming paint further comprises (F) 0.1 to 15 parts by mass of resin fine particles having an average particle size of 0.5 to 10 μm. The molded body according to claim 1, wherein the first hard coat has a thickness of 0.5 to 5 μm. The molded body according to claim 1, wherein the second hard coat has a thickness of 5 to 30 μm. A molded body comprising a resin substrate as follows:
The substrate has a three-dimensional shape,
Part or all of the surface of the substrate is covered with a hard coat,
The hard coat includes, from the surface layer side, a first hard coat layer and a second hard coat layer,
The first hard coat is formed from a paint containing no inorganic particles,
The second hard coat is formed from a paint containing inorganic particles,
the thickness of the first hard coat is 0.5 to 5 μm,
A molded body satisfying the following (i) and (ii):
(i) total light transmittance of at least 85%; and
(ii) Pencil hardness on the first hard coat surface of 5H or greater. A molded body comprising a resin substrate as follows:
The substrate has a three-dimensional shape,
Part or all of the surface of the substrate is covered with a hard coat,
The hard coat includes, from the surface layer side, a first hard coat layer and a second hard coat layer,
The first hard coat is formed from a paint containing no inorganic particles,
The second hard coat is formed from a paint containing inorganic particles,
Molded articles satisfying the following (iii) and (iv):
(iii) a water contact angle at the first hard coat surface of at least 100°; and
(iv) Water contact angle on the first hard coat surface after 20,000 reciprocating wipes on cotton, greater than 100°. The molded article according to claim 9 or 10, wherein the first hard coat is formed from a paint containing a water repellent and no inorganic particles. The molded article according to claim 11, wherein the water repellent agent comprises a (meth)acryloyl group-containing fluoropolyether water repellent agent. 11. Molded body according to any one of claims 1 to 10, wherein the substrate has a fully or partially printed layer on its surface. The molded body according to any one of claims 1 to 10, wherein the end portion has a chamfered shape. An article comprising the molded body according to any one of claims 1 to 10. A method for producing a shaped body according to any one of claims 1 to 10, comprising the following steps:
(1a) manufacturing a substrate by molding the resin sheet in three dimensions;
(2) forming a second hard coat on part or all of the surface of the substrate obtained in step (1a); and
(3) Forming a first hard coat on the surface of the second hard coat formed in step (2). The manufacturing method according to claim 16, wherein the resin sheet has a fully or partially printed layer on its surface. A method for producing a shaped body according to any one of claims 1 to 10, comprising the following steps:
(1b) manufacturing a substrate by molding a thermoplastic resin;
(2) forming a second hard coat on part or all of the surface of the substrate obtained in step (1b); and
(3) Forming a first hard coat on the surface of the second hard coat formed in step (2). A method for producing a shaped body according to any one of claims 1 to 10, comprising the following steps:
(1c) manufacturing a substrate by molding a curable resin;
(2) forming a second hard coat on part or all of the surface of the substrate obtained in step (1c); and
(3) Forming a first hard coat on the surface of the second hard coat formed in step (2). A method of making an article according to claim 15, comprising the following steps:
(1) manufacturing a substrate by three-dimensionally molding a resin sheet, molding a thermoplastic resin, or molding a curable resin;
(2) forming a second hard coat on part or all of the surface of the substrate obtained in step (1); and
(3) forming a first hard coat on the surface of the second hard coat formed in step (2) to obtain a molded body; and
(4) Manufacturing an article using the molded body obtained in step (3).

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